Efeito da oxidabilidade e susceptibilidade eletrofílica de compostos orgânicos aromáticos e fármacos em suas degradações por fotocatálise mediada por TiO2
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Data
2018-08-17
Autores
Spazzini, Fabíola Cristina Ricci
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Editor
Universidade Estadual Paulista (Unesp)
Resumo
A contaminação ambiental por efluentes orgânicos é atualmente um dos problemas ambientais mais sérios e, por conta disso, a eliminação desses poluentes tem sido largamente estudada. A degradação fotocatalítica mediada por dióxido de titânio (TiO2) de poluentes orgânicos, corantes e medicamentos é um assunto atual e intensamente investigado em ciências materiais e ambientais. Este processo é baseado em espécies reativas de oxigênio (EROs) geradas pela transferência de elétrons fotoinduzidos, provocando a oxidação da água e a redução do oxigênio dissolvido, levando à formação de radical hidroxila (HO●) e ânion superóxido (O2●-). Este trabalho teve como objetivo estudar a importância da susceptibilidade à oxidabilidade e ao ataque eletrofílico de compostos orgânicos em fármacos submetidos à degradação por fotocatálise mediada por TiO2. Para esse trabalho, a rodamina B foi utilizada como composto modelo para avaliar o efeito das EROs e moléculas orgânicas como o ácido salicílico, ácido benzóico, ácido protocatecúico, anisol, acetofenona e nitrobenzeno foram utilizados para avaliar a importância da susceptibilidade ao ataque eletrofílico e à oxidação. O TiO2 foi utilizado como catalisador em um meio constituído pelo analito pré-determinado, sob irradiação por luz ultravioleta (UVC, 6W). A reação foi monitorizada por 2,5 horas e as amostras foram removidas a intervalos de 30 minutos. A importância de cada EROs foi avaliada por desaeração do meio, adição de catalase, dimetilsulfóxido (DMSO), etanol e iodeto de potássio (KI), que foram utilizados para remoção de oxigênio dissolvido, peróxido de hidrogênio (H2O2), HO● e buracos na banda de valência, respectivamente. Verificou-se que o processo fotocatalítico não foi afetado pela desaeração, o que indicou que o O2 não foi relevante para a degradação da rodamina B. Resultados similares foram obtidos utilizando catalase, uma enzima capaz de degradar H2O2. A adição de KI provocou efeito inibitório significativo revelando a importância da formação dos buracos na banda de valência do semicondutor. O etanol demostrou-se como um inibidor potente, o que evidencia que os HO● foram a EROs mais relevante nesse estudo, enquanto que O2●-e H2O2 apresentaram-se menos efetivos perante as reações de fotodegradação. Em relação à classe de compostos analisados, verificou-se que a oxidabilidade dos compostos foi pouco relevante, pois todos foram eficientemente degradados. Com relação a susceptibilidade a ataque eletrofílico, verificou-se uma maior reatividade, embora sutil, à fotodegradação dos compostos mais reativos sob este aspecto. Não foi possível estabelecer um padrão de estrutura e reatividade para os fármacos estudados, pois o cetoprofeno foi susceptível a degradação mesmo na ausência de TiO2 e o paracetamol mostrou-se pouco reativo. Em conclusão, este texto apresenta um conjunto de resultados que podem ser úteis para pesquisadores que estudam processos de fotodegradação de compostos orgânicos.
Environmental contamination by organic effluents is currently one of the most serious environmental problems and, as a result, the elimination of these pollutants has been widely studied. Photocatalytic degradation mediated by titanium dioxide (TiO2) from organic pollutants, dyes and drugs is a current and intensely investigated subject in the environmental and material sciences. This process is based on reactive oxygen species (ROS) generated by photoinduced electron transfer, causing the oxidation of water and the reduction of dissolved oxygen, leading to the formation of hydroxyl radical (HO●) and superoxide anion (O2 ●- ). This work aimed to study the importance of the susceptibility to oxidation and electrophilic attack of organic compounds in drugs submitted to degradation by TiO2 mediated photocatalysis. For this work, rhodamine B was used as a model compound to evaluate the effect of EROs and organic molecules such as salicylic acid, benzoic acid, protocatechuic acid, anisole, acetophenone and nitrobenzene were used to evaluate the importance of susceptibility to electrophilic attack and oxidation. TiO2 was used as a catalyst in a medium consisting of the predetermined analyte, under ultraviolet light irradiation (UVC, 6W). The reaction was monitored for 2.5 hours and the samples were removed at 30 minute intervals. The importance of each ERO was evaluated by deaeration of the medium, addition of catalase, dimethylsulfoxide (DMSO), ethanol and potassium iodide (KI), which were used to remove dissolved oxygen, hydrogen peroxide (H2O2), HO● and holes in the valence band, respectively. It was found that the photocatalytic process was not affected by the deaeration, which indicated that O2 was not relevant for the degradation of rhodamine B. Similar results were obtained using catalase, an enzyme capable of degrading H2O2. The addition of KI caused a significant inhibitory effect revealing the importance of the formation of the holes in the semiconductor valence band. Ethanol was shown to be a potent inhibitor, which evidenced HOs where EROs were more important in this study, while their effects were more important than photodegradation reactions. In relation to the class of compounds analyzed, it was verified that the oxidability of the compounds was little relevant, since all were efficiently degraded. Regarding the susceptibility to electrophilic attack, a greater reactivity, although subtle, was verified to the photodegradation of the most reactive compounds in this aspect. It was not possible to establish a pattern of structure and reactivity for the drugs studied, since ketoprofen was susceptible to degradation even in the absence of TiO2 and paracetamol showed little reactivity. In conclusion, this text presents a set of results that may be useful for researchers studying processes of photodegradation of organic compounds.
Environmental contamination by organic effluents is currently one of the most serious environmental problems and, as a result, the elimination of these pollutants has been widely studied. Photocatalytic degradation mediated by titanium dioxide (TiO2) from organic pollutants, dyes and drugs is a current and intensely investigated subject in the environmental and material sciences. This process is based on reactive oxygen species (ROS) generated by photoinduced electron transfer, causing the oxidation of water and the reduction of dissolved oxygen, leading to the formation of hydroxyl radical (HO●) and superoxide anion (O2 ●- ). This work aimed to study the importance of the susceptibility to oxidation and electrophilic attack of organic compounds in drugs submitted to degradation by TiO2 mediated photocatalysis. For this work, rhodamine B was used as a model compound to evaluate the effect of EROs and organic molecules such as salicylic acid, benzoic acid, protocatechuic acid, anisole, acetophenone and nitrobenzene were used to evaluate the importance of susceptibility to electrophilic attack and oxidation. TiO2 was used as a catalyst in a medium consisting of the predetermined analyte, under ultraviolet light irradiation (UVC, 6W). The reaction was monitored for 2.5 hours and the samples were removed at 30 minute intervals. The importance of each ERO was evaluated by deaeration of the medium, addition of catalase, dimethylsulfoxide (DMSO), ethanol and potassium iodide (KI), which were used to remove dissolved oxygen, hydrogen peroxide (H2O2), HO● and holes in the valence band, respectively. It was found that the photocatalytic process was not affected by the deaeration, which indicated that O2 was not relevant for the degradation of rhodamine B. Similar results were obtained using catalase, an enzyme capable of degrading H2O2. The addition of KI caused a significant inhibitory effect revealing the importance of the formation of the holes in the semiconductor valence band. Ethanol was shown to be a potent inhibitor, which evidenced HOs where EROs were more important in this study, while their effects were more important than photodegradation reactions. In relation to the class of compounds analyzed, it was verified that the oxidability of the compounds was little relevant, since all were efficiently degraded. Regarding the susceptibility to electrophilic attack, a greater reactivity, although subtle, was verified to the photodegradation of the most reactive compounds in this aspect. It was not possible to establish a pattern of structure and reactivity for the drugs studied, since ketoprofen was susceptible to degradation even in the absence of TiO2 and paracetamol showed little reactivity. In conclusion, this text presents a set of results that may be useful for researchers studying processes of photodegradation of organic compounds.
Descrição
Palavras-chave
TiO2, Fotocatálise, EROS, Fotodegradação, Photocatalysis, Degradation